Multipole interactions in the molecular polarizabilities of water from ambient to high pressures

ORAL

Abstract

Knowledge of molecular polarizabilities in condensed phases provides important information about molecular crystals, and in general about materials composed of molecular or nano-building blocks. We propose a first-principles method based on electronic densities to compute molecular polarizabilities in condensed phases. The method includes all multipole interactions in addition to the dipole-dipole one, and it is applicable to any semiconductor or insulator. We present results for molecular polarizabilities of liquid water in a wide pressure-temperature range. We found that at ambient conditions, the dipole-induced-dipole approximation is sufficiently accurate and the Clausius-Mossotti relation may be used, e.g. to obtain molecular polarizabilities from experimental refractive indexes. However with increasing pressure this approximation becomes unreliable and in the case of ice X, where covalent bonds are present, the dipole-induced-dipole approximation breaks down.

*D. P. is supported by Hong Kong Research Grants Council (Project No. ECS-26305017), National Natural Science Foundation of China (Project No. 11774072). M. G. and G. G. are supported by the Midwest Integrated Center for Computational Materials (MICCoM).

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Presenters

  • Ding Pan

    • Department of Physics and Department of Chemistry, Hong Kong University of Science and Technology

Authors

  • Ding Pan

    • Department of Physics and Department of Chemistry, Hong Kong University of Science and Technology

  • Marco Govoni

    • Materials Science Division, Argonne National Laboratory
    • Institute for Molecular Engineering and Materials Science Division, Argonne National Lab
    • Argonne National Laboratory; University of Chicago
    • Insitute for Molecular Engineering and Materials Science Division, Argonne National Lab
    • Materials Science Division , Argonne National Laboratory
    • Argonne National Laboratory
    • Institute for Molecular Engineering, University of Chicago

  • Giulia Galli

    • Institute for Molecular Engineering, University of Chicago
    • Univ of Chicago
    • University of Chicago
    • Institute for Molecular Engineering, University of Chicago; Argonne National Laboratory
    • Institute for Molecular Engineering, University of Chicago, Chicago, IL, United States and Materials Science Division, Argonne National Laboratory
    • University of Chicago; Argonne National Laboratory
    • Institute for Molecular Engineering, Univ of Chicago